ES2346352T3 - POLYCARBONATE MOLDING MASSES. - Google Patents

Abstract

Composition containing A) a polycarbonate and / or aromatic polyester carbonate, B) if necessary an impact resistance modifier, C) where appropriate a homo and / or thermoplastic copolymer, D) a layered compound that is modified with poly (alkylene oxide) with a weight average molecular weight of 106 to 20,000 g / mol by means of a melt process without solvent, and E) if necessary a phosphorus compound.

Description

Molds of polycarbonate molding.

The invention relates to compositions of polycarbonate with improved thermal stability and speed of maximum maximum decomposition in case of fire.

Wang et al. report PC / ABS compositions (polycarbonate / acrylonitrile / butadiene / styrene) with high Thermal stability. In this case Montmorillonites of alkylammonium which were preferably distributed in the ABS phase (Wang, S., Hu, Y., Wang, Z., Yong, T., Chen, Z., & Fan, W., Synthesis and Characterization of polycarbonate / ABS / montmorillonite nanocomposites, Polymer Degradation and Stability, 80, No. 1, (2003) 157-61).

By Stretz et al. and Yoon et al. it is known that usual alkylammonium modifiers such as tallow-bis (2-hydroxyethyl) methylammonium,  as well as contained impurities (for example, iron ions) break down the polycarbonate matrix and increase, for example, the heat release rate (determined by calorimetry with cone) (Stretz, H. A., Koo, J. H., Dimas, V. M., & Zhang, Y., Flame retardant properties of polycarbonate / montmorillonite clay  nanocomposite blends, Polymer Preprints, 42, No. 2, (2001) 50; Yoon, P. J., Hunter, D. L., & Paul, D. R., Polycarbonate nanocomposites: Part 2. Degradation and color formation, Polymer, 44, No. 18, (2003) 5341-54).

The synergistic effect of the Montmorillonites of Alkylammonium for flame retardant properties is known by Wang and cabbage. for ABS molding masses (Wang, S., Hu, Y., Zong, R., Tang, Y., Chen, Z., & Fan, W., Preparation and characterization of flame retardant ABS / montmorillonite nanocomposite. Applied Clay Science, 25, No. 1-2, (2004) 49-55). Wang et al. they get improved flame retardant properties for ABS molded parts in combination with antimony oxide and decabromodiphenyl oxide. In the presence of the Montmorillonite of alkylammonium, the heat release rate (cone calorimeter) was reduced and a longer time was found until ignition, that is, the LOI (limiting oxygen index "Limiting oxygen index ") was higher and the fire behavior of the samples UL94 V was evaluated with the classification V-0

From WO 99/43747 A1 the synergistic effect for the flame retardant properties of montmorillonites of alkylammonium for PC / ABS compositions and it is taught that the time until the ignition of PC / ABS compositions is extended by adding clayton alkylammonium montmorillonite HY.

The disadvantage of Montmorillonites modified with alkylammonium are the complicated and expensive Philosilicate modification procedure. Phyllosilicates modified in this way also have a disadvantage in the physical properties of polycarbonate compositions since the basic phyllosilicate modifiers degrade the polymer and so lead to a decrease in the molecular weight of the polymer, as well as to opacity and coloration. In the procedure disclosed, works with unmodified phyllosilicates.

From US 2005/0137287 A1 polycarbonate compositions containing phyllosilicates are known which are modified with an ethyl 2- (dimethylamino) -styrene-methacrylate block polymer with a quaternary ammonium terminal group. The resulting polycarbonate molding masses are transparent and show no color.
tion.

By WO 99/07790 A1 and Fischer and cabbage. (Fischer, H. R., Gielgens, L. H., & Koster, T. P. M., Nanocomposites from polymers and layered minerals, Mat. Res. Soc. Proc. Vol 519, 1998, 117-123) materials are known nanocomposites that are constituted by block copolymers or graft and a phyllosilicate, the copolymer carrying a unit structural that is compatible with the phyllosilicate, as well as other unit that is compatible with the polymer matrix. The materials described compounds are prepared in a first stage by mixing of the phyllosilicate with high temperature copolymer and in a later stage by extrusion in the polymer matrix desirable. Alternatively, a solvent can also be added. Therefore, an improvement in tensile strength is achieved. of the modified material. PC / ABS compositions and procedures for modifying phyllosilicates by route watery

The disadvantages of modification through block copolymers are the complicated and expensive procedure of modification, as well as the need for a procedural stage additional for the synthesis of block copolymers.

The object of the invention is to provide polycarbonate molding masses with high thermal stability, a low maximum decomposition rate after ignition, as well as low smoke density.

It was surprisingly found that through the use of phyllosilicates, which are modified with poly (oxide of alkylene) with an average weighted molecular weight of 106 to 20,000 g / mol by a solvent-free melt process, increases thermal stability of molding masses containing polycarbonate and the maximum decomposition rate is reduced by case of fire The compositions according to the invention stand out because they don't use long chain quaternary ammonium salts like stabilizers and a degradation of the molecular weight of the polycarbonate, which also results in a high level of mechanical properties of the molding masses according to the invention.

Therefore, they are the subject of the present invention thermoplastic molding compositions or masses containing

TO)

a polycarbonate and / or polyester carbonate aromatic,

B)

if necessary a modifier of resistance to impact,

C)

if necessary a homo and / or copolymer thermoplastic,

D)

a layered compound that is modified with poly (alkylene oxide) with an average weighted molecular weight of 106 to 20,000 g / mol by a melt process without solvent, and

AND)

if necessary a phosphorus compound.

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Preferably, the compositions according to the invention contain

TO)

30 to 99.9 parts by weight, preferably 40 to 90 parts by weight of polycarbonate and / or polyester carbonate aromatic,

B)

0 to 60 parts by weight, preferably 1 to 40 parts by weight, especially preferably 2 to 15 parts by weight of a rubber modified graft polymer,

C)

0 to 30 parts by weight, preferably 0 to 25 parts by weight of homo and / or copolymer,

D)

0.1 to 40 parts by weight, preferably 1 to 25 parts by weight, especially preferably 2 to 10 parts by weight of a layered compound that is modified with poly (oxide of alkylene) with an average weighted molecular weight of 106 to 20,000 g / mol by a solvent-free melt process, Y

AND)

0 to 30 parts by weight, preferably 1 to 20 parts by weight, especially 4 to 15 parts by weight of compound of match.

All data of proportions by weight in the This application is standardized so that the sum of the parts by weight of the components A + B + C + D + E in the Composition is normalized to 100.

Suitable components according to the invention of Polycarbonate compositions are explained below to example mode.

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Component TO

According to the invention, aromatic polycarbonates and / or suitable aromatic polyester carbonates according to component A with known in the literature or can be prepared according to procedures known in the literature (for the preparation of aromatic polycarbonates see, for example, Schnell, "Chemistry and Physics of Polycarbonates ", Interscience Publishers, 1964, as well as documents DE-AS 1 495 626, DE-A 2 232 877, DE- A 2 703 376, DE-A 2 714 544, DE-A 3,000 610, DE-A 3 832 396; for the preparation of polyester aromatic carbonates, for example, the document DE-A 3 077 934).

The preparation of aromatic polycarbonates is performs, for example, by reacting diphenols with halides  of carbonic acid, preferably phosgene and / or dihalogenides of aromatic dicarboxylic acid, preferably dihalogenides of Benzenedicarboxylic acid, according to the interface procedure, if necessary using chain switches, for example, monophenols, and if necessary using trifunctional branching or more than trifunctional, for example triphels or tetraphenols. A preparation is also possible by means of a process of melt polymerization by reaction of diphenols with, for example, diphenylcarbonate.

Diphenols for the preparation of aromatic polycarbonates and / or polyester aromatic carbonates are preferably those of formula (I)

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one

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in the that

TO

means a single bond, C 1 alkylene C 5, C 2 to C 5 alkylidene, C 5 to cycloalkylidene C 6, -O-, -SO-, -CO-, -S-, -SO 2 -, C 6 arylene a C 12, to which other aromatic rings may be condensed which if necessary contain heteroatoms,

quad

or a remainder of formula (II) or (III)

2

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3

B

respectively means C 1 alkyl to C 12, preferably methyl, halogen, preferably chlorine and / or bromine,

x

means respectively regardless of yes, 0, 1 or 2,

p

they are 1 or 0, and

R 5 and R 6 selectable individually for each X1 independently mean with each other, hydrogen or C 1 to C 6 alkyl, preferably hydrogen, methyl or ethyl,

X1

means carbon and

m

means an integer from 4 to 7, preferably 4 or 5, with the proviso that at least one atom X1, R 5 and R 6 are both alkyl.

Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenols, bis- (hydroxyphenyl) -C 1 -C 5 alkanes, bis- (hi-
Droxyphenyl) -C 5 -C 6 -cycloalkanes, bis- (hydroxyphenyl), bis- (hydroxyphenyl) -sulfoxides, bis- (hydroxyphenyl) -ketones, bis- (hydroxyphenyl) -sulfones and α, α? -bis- (hydroxyphenyl) -diisopropyl-benzenes, as well as their brominated derivatives in the nucleus and / or chlorinated in the nucleus.

Especially preferred diphenols are 4,4'-dihydroxydiphenyl, bisphenol A, 2,4-bis- (4-hydroxyphenyl) -2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenyl sulfone as well as its di and tetrabromated or chlorinated derivatives, for example, 2,2-bis (3-chloro-4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane or 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) propane. It is especially preferred 2,2-bis- (4-hydroxyphenyl) propane (bisphenol-A).

Diphenols can be used separately or as discretionary mixes. Diphenols are known in the bibliography or can be obtained according to procedures known in the bibliography.

Chain switches suitable for Preparation of thermoplastic aromatic polycarbonates are, for example, phenol, p-chlorophenol and p-tert-butylphenol or 2,4,6-tribromophenol, but also alkylphenols of long chain like 4- [2- (2,4,4-trimethylpentyl)] - phenol, 4- (1,3-tetramethylbutyl) -phenol according DE-A 2 842 005 or monoalkylphenol or dialkylphenols with 8 to 20 carbon atoms in total in the alkyl substituents, such as 3,5-di-tert-butylphenol, p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol and 2- (3,5-dimethylheptyl) -phenol and 4- (3,5-dimethylheptyl) -phenol. The number of chain switches to be used amounts to general to between 0.5% in moles and 10% in moles, referred to the sum of moles of diphenols respectively used.

Thermoplastic aromatic polycarbonates they have average weight average molecular weights (M w, measured, for example, by ultracentrifuge or scattered light measurement) of 10,000 to 200,000 g / mol, preferably 15,000 to 80,000 g / mol, with special preference from 24,000 to 32,000 g / mol.

Thermoplastic aromatic polycarbonates they can be branched in a known way and specifically preferably by incorporating 0.05 to 2.0% in moles, referred to the sum of the diphenols used, of compounds trifunctional or more than trifunctional, for example those with Three and more phenolic groups.

Both homopolycarbonates and copolycarbonates For the preparation of copolycarbonates according to the invention according to component A can also be used from 1 to 25% by weight, preferably 2.5 to 25% by weight, based on the total amount of diphenols to be used, of polydiorganosiloxanes with terminal groups hydroxy-aryloxy. These are known (US 3 document 419 634) and can be prepared according to procedures known in the bibliography. The preparation of copolycarbonates containing Polydiorganosiloxanes is described in the document DE-A 3 334 782.

Preferred polycarbonates are, in addition to those bisphenol A homopolycarbonates, bisphenol copolycarbonates A with up to 15% in moles, referred to the amounts of moles of diphenols, of diphenols other than those mentioned as preferred or especially preferred, especially 2,2-bis (3,5-dibromo-4-hydroxyphenyl) -propane.

Dicarboxylic acid dihalogenides aromatic for the preparation of polyester aromatic carbonates are preferably isophthalic acid diacid dichlorides, terephthalic acid, acid diphenyl ether-4,4'-dicarboxylic and of the acid naphthalen-2,6-dicarboxylic.

Especially preferred are mixtures of the di-acid dichlorides of isophthalic acid and terephthalic acid in the ratio between 1:20 and 20: 1.

In the preparation of polyester carbonates are used together additionally a carbonic acid halide, preferably phosgene, as a derivative of bifunctional acid.

In addition to the monophenols already mentioned, such as chain switches for the preparation of polyester aromatic carbonates are also considered their esters of chlorocarbonic acid, as well as acid acid chlorides aromatic monocarboxylic acids that may be the case substituted with C 1 to C 22 alkyl groups, as well as C2 to C22 aliphatic monocarboxylic acid chlorides.

The number of chain switches amounts a respectively 0.1 to 10 mol%, referred in the case of the phenolic chain switches to moles of diphenol and in the case of monocarboxylic acid chloride chain switches moles of dicarboxylic acid dichloride.

The aromatic polyester carbonates also may contain incorporated hydroxycarboxylic acids aromatic

The aromatic polyester carbonates can be both linear and branched in a known way (for this see documents DE-A 2 940 024 and DE-A 3 007 934).

As branching agents they can be used, for example, tri or polyfunctional carboxylic acid chlorides, such as trimesinic acid trichloride, cyanuric acid trichloride, acid tetrachloride 3,3 ', 4,4'-benzophenone tetracarboxylic acid, tetrachloride of 1,4,5,8-naphthalentetracarboxylic acid or pyromellitic acid tetrachloride, in amounts of 0.01 to 1.0% in moles (referred to the dicarboxylic acid dichlorides used) or tri or polyfunctional phenols such as floroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hept-2-ene, 4,6-dimethyl-2,4-6-tri- (4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzene, 1,1,1-tri- (4-hydroxyphenyl) -ethane, tri- (4-hydroxyphenyl) -phenylmethane, 2,2-bis [4,4-bis (4-hydroxy-phenyl) -cyclohexyl] -propane, 2,4-bis (4-hydroxyphenyl-isopropyl) -phenol, tetra- (4-hydroxyphenyl) -methane, 2,6-bis (2-hydroxy-5-methyl-benzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) -propane, tetra- (4- [4-hydroxyphenyl-isopropyl] -phenoxy) -methane, 1,4-bis [4,4'-dihydroxytri-phenyl) -methyl] -benzene,  in amounts of 0.01 to 1.0 mol% referred to diphenols used. Phenolic branching agents can be arranged with diphenols, acid chloride branching agents they can be introduced together with acid dichlorides.

In aromatic polyester carbonates thermoplastics can be discretionally varied the proportion of carbonate structural units. The proportion of groups carbonate preferably amounts to 100 mol%, especially up to 80 mol%, with special preference up to 50 mol%, based on the sum of ester groups and groups carbonate. The proportion of both ester and carbonate of the polyester aromatic carbonates can be presented in the form of blocks or statistically distributed in the polycondensate.

The relative viscosity in solution (\ eta_ {rel}) of polycarbonates and polyester carbonates aromatic is in the range of 1.18 to 1.4, preferably 1.20 at 1.35 (measured in solutions of 0.5 g of polycarbonate or polyester carbonate in 100 ml of methylene chloride solution a 25 ° C).

Polycarbonates and polyester carbonates thermoplastic aromatics can be used alone or in a mixture discretionary

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Component B

Component B comprises one or more polymers graft of

B.1

5 to 95, preferably 30 to 90% by weight of at least one vinyl monomer in

B.2

95 to 5, preferably 70 to 10% by weight of one or more graft bases with glass transition temperatures <10 ° C, preferably <0 ° C, especially < -20 ° C.

The graft base B.2 generally has a average particle size (d 50 value) from 0.05 to 10 µm, preferably 0.1 to 5 µm, especially preferably 0.2 to 1 \ mum.

B.1 monomers are preferably mixtures from

B.1.1

50 to 99 parts by weight of aromatic compounds of vinyl and / or vinyl aromatic compounds substituted at the core (such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene) and / or (C 1 -C 8) alkyl esters of acid methacrylic as methyl methacrylate, ethyl methacrylate, Y

B.1.2

1 to 50 parts by weight of vinyl cyanides (unsaturated nitriles such as acrylonitrile and methacrylonitrile) and / or (C 1 -C 8) alkyl esters of acid (meth) acrylic as methyl methacrylate, acrylate n-butyl, t-butyl acrylate and / or derivatives (such as anhydrides and imides) of carboxylic acids unsaturated, for example, maleic acid anhydride and N-phenyl-maleinimide.

Preferred B.1.1 monomers are selected from at least one of the styrene monomers, α-methylstyrene and methyl methacrylate, Preferred B.1.2 monomers are selected from at least one of the acrylonitrile monomers, maleic acid anhydride and methacrylate of methyl Especially preferred monomers are B.1.1 styrene and B.1.2 acrylonitrile.

B.2 graft bases suitable for graft B polymers are, for example, diene rubbers, rubbers of EP (D) M, that is, those based on ethylene / propylene and, where appropriate, diene, acrylate rubbers, polyurethane, silicone, chloroprene and ethylene / vinyl acetate.

Preferred graft bases B.2 are rubbers dienics, for example, based on butadiene and isoprene, or mixtures of diene rubbers or copolymers of diene rubbers or mixtures thereof with other copolymerizable monomers (for example according to B.1.1 and B.1.2), with the proviso that the glass transition temperature of component B.2 is below <10 ° C, preferably <0 ° C, especially <-10 ° C. Be He especially prefers pure polybutadiene rubber.

Especially preferred B polymers are, for example, ABS polymers (emulsion, mass and suspension ABS) as described, for example, in the document DE-OS 2 035 390 (= US-PS 3 644 574) or in DE-OS 2 248 242 (= GB-PS 1 409 275) or in Ullmanns Enzyklopädie der Technischen Chemie, Volume 19 (1980), p. 280 and following. The proportion of graft base gel B.2 amounts to at least 30% by weight, preferably at least 40% by weight (measured in Toluene).

Graft B copolymers are prepared by radical polymerization, for example, by emulsion, suspension, solution or mass polymerization, preferably by emulsion or mass polymerization.

They are also graft rubbers especially suitable ABS polymers that are prepared in the process of emulsion polymerization by redox initiation with a system organic hydroperoxide and ascorbic acid initiator according to US-P 4 937 285.

As in the grafting reaction the monomers of graft do not necessarily graft completely at the base of graft, according to the invention are also understood as polymers of graft B those products that are obtained by (co) polymerization of graft monomers in the presence of the graft base and that occur concomitantly in the transformation.

Suitable acrylate rubbers according to B.2 of polymers B are preferably polymers of alkyl esters of acrylic acid, if necessary with up to 40% by weight, based on B.2, of other polymerizable ethylenically unsaturated monomers. To the preferred polymerizable acrylic acid esters belong C 1 to C 8 alkyl esters, for example methyl ester, ethyl, butyl, n-octyl and 2-ethylhexyl; halogenoalkyl esters, preferably halogenoalkyl esters C 1 -C 8 as chloroethyl acrylate, as well as mixtures of these monomers.

For crosslinking they can be copolymerized monomers with more than one polymerizable double bond. Examples Preferred crosslinking monomers are acid esters unsaturated monocarboxylic acids with 3 to 8 C atoms and alcohols unsaturated monohydroxy with 3 to 12 C atoms, or polyols saturated with 2 to 4 OH groups and 2 to 20 C atoms as ethylene glycol dimethacrylate, allyl methacrylate; compounds polyunsaturated heterocyclics such as trivinyl cyanurate and trialyl; polyfunctional vinyl compounds such as di and trivinylbenzenes; but also triallyl phosphate and phthalate diallyl Preferred crosslinking monomers are methacrylate of allyl, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds having at least three groups ethylenically unsaturated. Crosslinking monomers especially Preferred are the cyclic monomers of triallyl cyanurate, triallyl isocyanurate, triacryloylhexahydro-s-triazine, trialylbenzenes. The amount of crosslinking monomers amounts to preferably at 0.02 to 5, especially 0.05 to 2% in weight, based on graft base B.2. In the case of monomers cyclic crosslinkers with at least three ethylenically groups unsaturated it is advantageous to limit the amount to less than 1% by weight of the graft base B.2.

"Other" ethylenically monomers preferred polymerizable unsaturates that may be the case serve, in addition to the esters of acrylic acid, for Preparation of graft base B.2 are, for example, acrylonitrile, styrene, α-methylstyrene, acrylamides, C 1 -C 6 vinyl alkyl ethers, methyl methacrylate, butadiene. Acrylate rubbers Preferred as graft base B.2 are emulsion polymers that they have a gel content of at least 60% by weight.

Other suitable graft bases according to B.2 are silicone rubbers with active sites for grafting as described in DE-OS 3 704 657, DE-OS 3 704 655, DE-OS 3 631 540 and DE-OS 3 631 539.

The gel content of the graft base B.2 is determined at 25 ° C in a suitable solvent (M. Hoffmann, H. Krömer, R. Kuhn, Polymeranalytik I und II, Georg Thieme editorial, Stuttgart 1977).

The average particle size d_ {50} is the diameter above and below which are respectively the 50% by weight of the particles. It can be determined by measurement in ultracentrifuge (W. Scholtan, H. Lange, Kolloid, Z. und Z. Polymere 250 (1972), 782-1796).

Graft polymers can be used in the composition according to the invention in an amount of 0.5 to 60, preferably 1 to 40 and most preferably 2 to 25 parts in weight. Mixtures of different polymers may also be present. graft

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Component C

Component C comprises one or more (co) C.1 and / or thermoplastic vinyl polymers poly (alkylene terephthalates) C.2.

As (co) C.1 vinyl polymers are suitable polymers of at least one monomer of the group of aromatic vinyl compounds, vinyl cyanides (nitriles unsaturated), alkyl esters (C 1 -C 8) of (meth) acrylic acid, unsaturated carboxylic acids, as well as derivatives (as anhydrides and imides) of carboxylic acids unsaturated Especially suitable are (co) polymers of

C.1.1

50 to 99, preferably 60 to 80 parts by weight, of aromatic vinyl compounds and / or aromatic vinyl compounds substituted in the nucleus such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene and / or (C 1 -C 8) alkyl esters of acid (meth) acrylic such as methyl methacrylate, ethyl methacrylate, and

C.1.2

1 to 50, preferably 20 to 40 parts by weight, of vinyl cyanides (unsaturated nitriles) such as acrylonitrile and methacrylonitrile and / or alkyl esters (C 1 -C 8) of (meth) acrylic acid as methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and / or carboxylic acids unsaturated, such as maleic acid, and / or derivatives, such as anhydrides and imides, of unsaturated carboxylic acids, for example, anhydride of maleic acid and N-phenylmaleinimide.

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The C.1 (co) polymers are resiniform, thermoplastics and rubber free. The copolymer is especially preferred.  of C.1.1 styrene and C.1.2 acrylonitrile.

The (co) polymers according to C.1 are known and can be prepared by radical polymerization, especially by emulsion polymerization, suspension, dissolution or mass. The (co) polymers possess preferably molecular weights M W (average by weight, determined by light scattering or sedimentation) between 15,000 and 200,000.

The poly (alkylene terephthalates) of component C.2 are reaction products of dicarboxylic acids aromatics or their reactive derivatives, such as dimethyl esters or anhydrides, and aliphatic, cycloaliphatic or araliphatic diols, as well as mixtures of these reaction products.

Poly (alkylene terephthalates) Preferred contain at least 80% by weight, preferably at minus 90% by weight, based on the acid component dicarboxylic, of terephthalic acid residues and at least 80% in weight, preferably at least 90 mol%, based on diol component, ethylene glycol residues and / or 1,4-butanediol and / or 1,3-propanediol.

Poly (alkylene terephthalates) Preferred may contain, in addition to terephthalic acid moieties, up to 20 mol%, preferably up to 10 mol%, of residues of other aromatic or cycloaliphatic dicarboxylic acids with 8 to 14 C atoms or aliphatic dicarboxylic acids with 4 to 12 C atoms such as phthalic acid residues, acid isophthalic acid naphthalen-2,6-dicarboxylic acid 4,4'-diphenyldicarboxylic acid, succinic acid, acid adipic acid, sebacic acid, azelaic acid, acid cyclohexanediacetic.

Poly (alkylene terephthalates) Preferred may contain, in addition to ethylene glycol moieties or 1,4-butanediol, up to 20 mol%, preferably up to 10 mol% of other aliphatic diols with 3 to 12 C atoms or cycloaliphatic diols with 6 to 21 atoms of C, for example 1,3-propanediol moieties, 2-ethyl-1,3-propanediol,  neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 3-ethyl-2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,2-diethyl-1,3-propanediol, 2,5-hexanediol, 1,4-di - (β-hydroxyethoxy) -benzene, 2,2-bis- (4-hydroxycyclohexyl) -propane, 2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane, 2,2-bis- (4-? -Hydroxyethoxyphenyl) -propane  Y 2,2-bis- (4-hydroxypropoxyphenyl) -propane (documents DE-A 2 407 674, 2 407 776, 2 715 932).

Poly (alkylene terephthalates) can be branched by entering relatively quantities small of tri or tetrahydroxy alcohols or carboxylic acids tri or tetrabasic, for example according to the documents DE-A 1 900 270 and US-PS 3 692 744. Examples of preferred branching agents are acidic. trimesinic, trimellitic acid, trimethylolethane and trimethylolpropane and pentaerythritol.

They are especially preferred poly (alkylene terephthalates) that have been prepared only at starting from terephthalic acid and its reactive derivatives (for example, its dialkyl esters) and ethylene glycol and / or 1,4-butanediol, and mixtures thereof poly (alkylene terephthalates).

Mixtures of poly (terephthalates from alkylene) contain from 1 to 50% by weight, preferably from 1 to 30% by weight, of poly (ethylene terephthalate) and 50 to 99% by weight, preferably 70 to 99% by weight, of poly (butylene terephthalate).

Poly (alkylene terephthalates) preferably used generally have a viscosity limit of 0.4 to 1.5 dl / g, preferably 0.5 to 1.2 dl / g, measured in phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C in the Ubbelohde viscometer.

Poly (alkylene terephthalates) they can be prepared according to known procedures (see, for example, Kunststoff Handbuch, volume VIII, p. 695 and following, Carl-Hanser editorial, Munich 1973).

The (co) polymers of vinyl or poly (alkylene terephthalates) may be contained in amounts from 0 to 45, preferably 1 to 30 and with special preference 2 to 25 parts by weight in the composition according to the invention.

Component D

Component D comprises layered compounds which are modified with poly (alkylene oxide) with a weight Weighted average molecular weight of 106 to 20,000 g / mol by a process in molten mass without solvent.

Layered compounds in the direction according to invention are preferably layered compounds that are in a dimension at nanometric scale, that is, less than 100 nm. This dimension is referred to below as "average thickness" of layered compound. Those compounds are preferably used in layers with an average thickness of 0.3 to 10 nm, with special preferably 0.5 to 10 nm, especially preferably 0.7 to 2 nm The layers have a diameter of 5 to 10,000 nm, preferably from 10 to 2000 nm, especially preferably from 10 to 1000 nm The cation exchange capabilities of the compounds in unmodified anionic layers are between 10 and 260 meq / 100 g Counterions (i.e. cation) of compounds unmodified layers can be calcium, magnesium, potassium ions, sodium, lithium, preferably sodium or lithium ions. These cations they can come, for example, or from natural (geological) sources in those that contain commercial minerals, or incorporated specifically by ion exchange as described by Lagaly (Lagaly, G., Reaktionen der Tonminerale in Tonminerale und Tone, Steinkopff Verlag, Darmstadt, 1993). The size of the layered compounds (i.e. the diameter or average thickness of the layers of the compound in layers) can be determined by TEM photographs and XRD measurements: the determination of cation exchange capacity can be realized, for example, according to L. P. Meier and G. Kahr (Clays & Clay Minerals, 1999, 47, 3, p. 386-388).

As layered compounds are used for this compounds in synthetic layers as well as of natural origin. Compounds in mineral type layers are preferably used Montmorillonite, hectorite, as well as the phyllosilicates or clay minerals alevardite, amesite, beidellite, fluorohectorite, fluorovermiculite, mica, halloysite, hectorite, ilita, montmorillonite, muscovite, nontronite, paligorskite, saponite, sepiolite, smectite, estevensite, talcum powder, vermiculite, types of synthetic talc and alkali silicates maghemite, magadiita, keniaita, makatita, silinaita, grumantita, revdita, thus as its hydrated forms and crystalline silicic acids corresponding or other compounds in inorganic layers such as hydrotalcite, double hydroxides and heteropoly acids.

As layered compounds they are used with special preference layered compounds containing silicates. Are used especially preferably compounds in layers containing silicates of the type of montmorillonite minerals as they are contained as the main constituent in bentonite, as well as hectorite, that have a cation exchange capacity between 10 and 260 meq / 100 g, an average thickness of 0.3 to 10 nm, with special preferably 0.5 to 10 nm, especially preferably 0.7 to 2 nm, and a diameter of the layers of 5 to 10,000 nm, preferably of 10 to 2000 nm, especially preferably 10 to 1000 nm.

According to the invention, the layered compound is modified with at least poly (alkylene oxide) with a weight Weighted average molecular weight of 106 to 20,000 g / mol by a process in molten mass without solvent. In this regard

(i)

in a first stage, the layered compound is mixture with poly (alkylene oxide) with a weighted molecular weight medium 106 to 20,000 g / mol or a mixture of poly (alkylene oxide) with an average weighted molecular weight of 106 to 20,000 g / mol and others organic polymers,

(ii)

in a second stage, the mixture is heated to a temperature above the melting temperature of the poly (oxide alkylene) used with a weight average molecular weight of 106 to 20,000 g / mol or the mixture of polymers used of poly (oxide of alkylene) with an average weighted molecular weight of 106 to 20,000 g / mol and at least one other organic polymer, preferably with continuous stirring, for example, by an internal mixer or an extruder press, and

(iii)

if necessary, in a third stage, the mixture of (ii) cooled to room temperature and the layered compound Modified is obtained in the form of a solid.

Alternatively, the heated mixture that results of step (ii) can be incorporated as such in the polycarbonate composition according to the invention, for example, by means of a lateral extruder press.

For this modification poly (oxides of alkylene) as organic polymers. These poly (alkylene oxides)  they have an average weighted molecular weight of 106 to 20,000 g / mol, with special preference of 200 to 10000 g / mol, being able to be used also mixtures of different poly (alkylene oxides). How poly (alkylene oxides) are preferably used poly (oxides of ethylene) and copolymers of poly (ethylene oxide) -propylene oxide.  Linear poly (ethylene oxides) are used with particular preference and very especially preferably monomethyl ethers of poly (ethylene glycol).

If necessary, in step (i) they can also other suitable oligomers or polymers are added. For this it is used preferably polycarbonate (component A) and / or poly (methyl methacrylate) (PMMA).

Component AND

Phosphorus-containing flame retardants (E) in the sense according to the invention they are preferably selected from the groups of mono and phosphonic acid esters and oligomers, phosphonateamines and phosphazenes, and can also be used as flame retardant agents mixtures of various selected components of one or more of these groups. Compounds of halogen-free phosphorus not especially mentioned in this document alone or in discretionary combination with other compounds phosphorus without halogens.

Mono phosphoric acid or phosphonic acid esters and preferred oligomers are phosphorus compounds of formula general (IV)

4

in the that

R1, R2, R3 and R4  mean, independently of each other, respectively alkyl C_ {{{{}}} to C_ {{{}}})), respectively C5 to C6 cycloalkyl, C6 to C20 aryl or C 7 to C 12 aralkyl, where appropriate substituted by alkyl, preferably C 1 to C 4 alkyl, and / or halogen, preferably chlorine, bromine,

n

means, independently of each other, 0 or one

that

means 0 to 30 and

X

means an aromatic residue of one or more nuclei with 6 to 30 C atoms, or a linear or branched aliphatic moiety with 2 to 30 C atoms, which may be substituted with OH and contain Up to 8 ether links.

Preferably, R 1, R 2, R 3 and R 4 represent, independently of each other, C 1 to C 4 alkyl, phenyl, naphthyl or phenyl-C_ alkyl {1} -C_ {4}. The aromatic groups R 1, R 2, R 3 and R 4 may in turn be substituted with halogen and / or alkyl groups, preferably chlorine, bromine and / or C 1 alkyl 1} to C4. Especially preferred aryl moieties are cresyl, phenyl, xylenyl, propylphenyl or butylphenyl, as well as the corresponding brominated and chlorinated derivatives of the
same.

X

in formula (IV) it preferably means a aromatic residue of one or more nuclei with 6 to 30 C atoms. This is preferably derived from diphenols of formula (I).

n

in formula (IV) it can be independently with each other, 0 or 1, preferably n is equal to 1.

that

represents values from 0 to 30. In the use of mixtures of different components of formula (IV) can be used preferably mixtures of values of q weighted average of 0.3 to 10, especially preferably 0.5 to 10, especially 0.5 to 6.

X

represents with special preference

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5

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or its chlorinated derivatives or brominated, X is especially derived from resorcinol, hydroquinone, bisphenol A or diphenylphenol. X is derived with special preference of bisphenol TO.

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The use of phosphoric acid esters oligomers of formula (IV) that are derived from bisphenol A is especially advantageous since the compositions containing this Phosphorus compound exhibit tensile strength and especially high hydrolysis, as well as a tendency especially low to the formation of layers in the processing of injection molding. In addition, with these flame retardants you can achieve dimensional heat stability especially high.

As component E according to the invention they can monophosphates (q = 0), oligophosphates (q = 1-30) or mixtures of mono and oligophosphates.

The monophosphorus compounds of formula (IV) They are especially tributyl phosphate, phosphate tris- (2-chloroethyl) phosphate tris- (2,3-dibromopropyl), triphenyl phosphate, tricresyl phosphate, diphenylcresyl phosphate, diphenyloctyl phosphate diphenyl-2-ethylcresyl phosphate tri (isopropylphenyl), aryl phosphates substituted with halogen, methylphosphonic acid dimethyl esters, esters diphenyl of methylphosphic acid, diethyl esters of acid phenylphosphonic, triphenylphosphine oxide or tricresylphosphine

Phosphorus compounds according to component E, formula (IV), are known (see, for example, documents EP-A 363 608, EP-A 640 655) or can be prepared analogously according to known procedures (for example, Ullmanns Encyklopädie der technischen Chemie, volume 18, P. 301 and following 1979; Houben-Weyl, Methoden der Organischen Chemie, volume 12/1, p. 43; Beilstein volume 6, p. 177).

The average q values can be determined determining the composition of the phosphate mixture (dispersion of molecular weights) by appropriate procedures (chromatography gas (GC), high pressure liquid chromatography (HPLC), molecular exclusion chromatography (GPC) and calculating from these average values for q.

The phosphonateamines are preferably compounds of formula (V)

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6

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in the that

TO

represents a remainder of formula (Va)

7

or (Vb)

8

R 11 and R 12 represent, independently of each other, alkyl C 1 -C 10 unsubstituted or substituted or aryl C_ {6} to C_ {10} without replacing or replaced,

R 13 and R 14 represent, independently of each other, C 1 to C 10 alkyl without substituted or substituted or C 6 to C 10 aryl unsubstituted or replaced,

R 13 and R 14 represent together C3 to C10 alkylene unsubstituted or replaced,

Y

means the numerical values 0, 1 or 2 Y

B1

independently represents hydrogen, alkyl C 2 to C 8, if halogenated, aryl C 6 to C 10 unsubstituted or substituted,

B1

preferably independently represents hydrogen, ethyl, n- or iso-propyl, which may be  halogen substituted, C 6 to C 10 aryl unsubstituted or substituted with C 1 to C 4 alkyl and / or halogen, especially phenyl or naphthyl.

Alkyl in R 11, R 12, R 13 and R 14 independently represents preferably methyl, ethyl, n-propyl, iso-propyl, n-, iso-, sec- or tert-butyl, pentyl or hexyl.

Alkyl substituted at R 11, R 12, R 13 and R 14 independently independently represents preferably C 1 to C 10 alkyl substituted by halogen, especially methyl, ethyl, n-propyl, iso-propyl, n-, iso-, sec- o tert-butyl, pentyl or substituted hexyl one or two times.

Aryl C 6 to C 10 represents in R 11, R 12, R 13 and R 14 independently preferably phenyl, naphthyl or binaphthyl, especially o-phenyl, o-naphthyl, o-binaphthyl, which can be substituted with halogen (generally one, two or three times).

R 13 and R 14 can form a structure ring together with the oxygen atoms to which they are directly attached and the phosphorus atom.

By way of example and preferably they are of to mention: 5,5,5 ', 5', 5 '', 5 '' - hexamethyltris (1,3,2-dioxafosforinan-methane) amino-2,2 ', 2' '- trioxide  of formula (Va-1)

9

1,3,2-Dioxafosforinan-2-methanamine, N-butyl-N [(5,5-dimethyl-1,3,2-dioxafosforinan-2-yl) -methyl] -5,5-dimethyl-, P, 2-dioxides; 1,3,2-dioxafosforinan-2-methanamine, N - [[5,5-dimethyl-1,3,2-dioxafosforinan-2-yl) methyl] -5,5-dimethyl-N-phenyl-, P, 2-dioxide; 1,3,2-dioxaphosphorin-2-methanamine, N, N-dibutyl-5,5-dimethyl-, 2-oxide, 1,3,2-dioxaphosphorin-2-methanimine, N - [(5,5-dimethyl -1,3,2-dioxaphosphonan-2-yl) methyl] -N-ethyl-5,5-dimethyl-, P, 2-dioxide, 1,3,2-dioxaphosphorin-2-methanamine, N-butyl-N - [(5,5-Dichloromethyl-1,3,2, dioxaphosphorinan-2-yl) -methyl] -5,5-di-chloromethyl-, P, 2-dioxide, 1,3,2-dioxaphosphorin-2- methanamine, N - [(5,5-dichloromethyl-1,3,2-dioxaphosphorinan-2-yl) methyl] -5,5-di-chloromethyl-N-phenyl-, P, 2-
dioxide; 1,3,2-dioxaphosphorin-2-methanamine, N, N-di- (4-chlorobutyl) -5,5-dimethyl-2-oxides; 1,3,2-dioxafosforinan-2-methanimine, N - [(5,5-dimethyl-1,3,2-dioxafosforinan-2-yl) methan] -N- (2-chloroethyl) -5,5-di (chloromethyl) -, P2-dioxide.

They are further preferred:

compounds of formula (Va-2) or (Va-3)

10

eleven

in the that

R 11, R 12, R 13 and R 14 have the meanings specified above.

Compounds of formula are especially preferred (Va-2) and (Va-1). The preparation of phosphonateamines are described, for example, in the document US-PS 5 844 028.

Phosphazenes are compounds of formulas (VIa) and (VIb)

12

13

in the that

R

is respectively the same or different and represents amino, respectively C 1 to C 8 alkyl, or C 1 alkoxy to C 8, where appropriate halogenated, preferably halogenated with fluorine, respectively C5 to C6 cycloalkyl if necessary substituted by alkyl, preferably C 1 to C 4 alkyl, and / or halogen, preferably chlorine and / or bromine, C6 aryl a C20, preferably phenyl or naphthyl, C6 aryloxy a C 20, preferably phenoxy, naphthyloxy, or C 7 aralkyl at C 12, preferably phenyl-alkyl C_ {1} -C_ {{}},

k

represents 0 or a number from 1 to 15, preferably represents a number from 1 to 10.

By way of example they are to mention propoxyphosphazene, phenoxyphosphazene, methylphenoxyphosphazene, aminophosphazene and fluoroalkylphosphazene. It preferred phenoxyphosphazene

Phosphazenes can be used alone or as mixture. The remainder R may always be the same or 2 or more residues in the formulas (Ia) and (Ib) may be different. The phosphazenes and their preparation are described, for example, in the documents EP-A 728 811, DE-A 1 961668 and WO 97/40092.

Flame retardants can be used alone or in discretionary mixing with each other or in admixture with other agents flame retardant Phosphorus-containing flame retardants can be used. in an amount of 0.1 to 30, preferably 1 to 25 and at most preferred 2 to 20 parts by weight in the composition according to the invention.

Component F

The flame retardants corresponding to component E are often used in combination with the so-called anti-drip agents that decrease the tendency of the material to formation of burning drops in case of fire. As an example It is worth mentioning in this case compounds of the substance classes of fluorinated polyolefins, of silicones, as well as fibers of aramid These can also be used in the compositions according to invention. As anti-drip agents they are preferably used fluorinated polyolefins. The fluorinated polyolefins are contained in general in an amount of 0.01 to 3, preferably 0.05 to 1.5 parts by weight in the mixture.

The fluorinated polyolefins are known and are described, for example, in EP-A 0 640 655. They are marketed under the Teflon® brand, for example, Teflon 30N from DuPont.

Fluorinated polyolefins can be used both in pure form as well as in the form of a coagulated mixture of emulsions of fluorinated polyolefins with emulsions of graft polymers (component B) or with an emulsion of a copolymer, preferably based on styrene / acrylonitrile, mixing fluorinated polyolefin as an emulsion with an emulsion of the graft polymer or copolymer and then coagulating

In addition, fluorinated polyolefins can be used as precomposed with the graft polymer (component B) or a copolymer, preferably based on styrene / acrylonitrile. The fluorinated polyolefins are mixed as a powder with a powder or granule of the graft polymer or copolymer and combine in the dough melted in general at temperatures of 200 to 330 ° C in units Common as internal kneaders, extruders or screws double spindle.

Fluorinated polyolefins can also be used in the form of a mother mixture that is prepared by polymerization in emulsion of at least one monoethylenically unsaturated monomer in presence of an aqueous dispersion of the fluorinated polyolefin. The Preferred monomer components are styrene, acrylonitrile and their mixtures The polymer is used after acid precipitation and subsequent drying as loose powder.

Clots, precomposites or mother mixtures they usually have fluorinated polyolefin solids contents 5 to 95% by weight, preferably 7 to 60% by weight.

Component G

In addition, the composition may contain other polymer additives (component G) as flame retardants, lubricants and mold release agents, for example, tetraestearate pentaerythritol, nucleating agents, antistatic agents, stabilizers, fillers and reinforcing substances (for example, glass or carbon fibers; mica, kaolin, talc, CaCO3 and glass flakes), as well as dyes and pigments.

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Preparation of molding doughs and molded bodies

Thermoplastic molding masses according to the invention are prepared by mixing in known manner the respective constituents and combining them in melt and extruding them in molten mass at temperatures of 200ºC to 300ºC in usual units such as internal mixers, extruder presses or double spindle screws.

The mixing of the different constituents it can be done in a known way both successively and simultaneously, and specifically both at approximately 20 ° C (room temperature) as at higher temperature.

In a preferred embodiment

(i)

in a first stage, the layered compound is modifies with poly (alkylene oxides) with a molecular weight weighted average of 106 to 20,000 g / mol, preferably 200 to 10,000 g / mol, by a solvent-free melt process, being able to mixtures of different poly (oxides of alkylene),

(ii)

in a second stage, the compound mixture layered obtained from (i) is mixed in a known manner with component (A) and if necessary other components selected from the group of (B), (C), (E), (F) and (G) and

(iii)

In a third stage, the mixture of (ii) is combined in molten mass and extruded in molten mass at temperatures of 200ºC to 300ºC in usual units as internal mixers, extruder presses and double screw screws,

being able to isolate the parent mixture of the compound layered resulting in the first stage (i) or may also processed directly as a melt, preferably with a lateral extruder press, in the stage molding mass (ii).

In an embodiment especially preferred, in the first stage (i) other oligomers are used or polymers selected from the group consisting of polycarbonate (according to component A) and poly (methyl methacrylate) (PMMA)

Thermoplastic molding masses according to the invention are suitable due to its high thermal stability and its good mechanical properties for body manufacturing molded of any kind, especially those with high requirements for maximum heat release rates.

The molding masses according to the invention can be used for the preparation of molded bodies of any kind. These can be manufactured by injection molding, extrusion and blow molding procedure. Another form of processing is the manufacture of molded bodies by deep drawing to from the plates or sheets previously manufactured.

Therefore, it is also another object of the present invention the use of molding masses according to the invention for the preparation of molded bodies of any kind, preferably of the aforementioned, as well as the molded bodies of the molding masses according to the invention.

Examples of such molded bodies are sheets, profiles, housing parts of any kind, for example for appliances such as juicers, coffee machines, blenders; for office machines such as monitors, flat screens, laptops, printers, photocopiers; plates, tubes, channels for electrical installations, windows, doors and others profiles for the construction sector (construction of interior and exterior applications) as well as components electrical and electronic like switches, plugs and plugs and components for industrial vehicles, especially for the automotive sector

The molding masses according to the invention also they can be used especially, for example, for the manufacture of The following molded bodies: interior installation parts for vehicles on rails, ships, airplanes, buses and others automobiles, electrical device housings containing small transformers, housings for devices for information processing and transmission, housings and coatings of medical devices, massage devices and housings for them, children's toy vehicles, wall panels flat, housings for safety devices, containers transport heat-insulated, molded parts for equipment sanitary and bathroom, protection grilles for holes ventilation and housings for gardening tools.

The following examples serve to explain additionally the invention.

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Examples

Component A1

Branched polycarbonate based on bisphenol A with a relative viscosity in solution of 1.34 measured in chloride of methylene at 25 ° C and at a concentration of 0.5 g / 100 ml

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Component A2

Linear polycarbonate based on bisphenol A with a relative viscosity in solution of 1.20 measured in chloride of methylene at 25 ° C and at a concentration of 0.5 g / 100 ml

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Component B

ABS polymer prepared by 43% by weight emulsion polymerization based on the polymer of ABS of a mixture of 27% by weight of acrylonitrile and 73% by weight of styrene in the presence of 57% by weight based on the ABS polymer of a particulate crosslinked polybutadiene rubber (mean diameter of particle d 50 = 0.35 µm).

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Component D1

Cationically Modified Phosilicate (modified with stearylbenzyl dimethyl ammonium chloride) (Nanofil 9, powder, specific gravity about 1.8 g / cm3, average size 8 µm particle size, primary particle size at dispersion complete approximately 100-500 nm x 1 nm, manufacturer Süd-Chemie AG).

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Component D2

Phyllosilicate-polycarbonate master mix (according to the invention)

For the preparation of the mother mixture of phyllosilicate-polycarbonate substances Item cited in Table 1 are kneaded in a micro press 10 ml extruder (company DSM) at 240 ° C for 5 minutes, they are left  stand and cool to room temperature.

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TABLE 1

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14

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Component D2-1

Nanofil 757 (high sodium montmorillonite purity, powder, specific gravity about 2.6 g / cm3, average particle size <10 \ mum, particle size primary to full dispersion approximately 500 nm x 1 nm, manufacturer Süd-Chemie AG). The sizes are determined by TEM photography and XRD measurements: thickness 1 nm layer medium and layer diameter of approximately 300 - 1000 nm

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Component D2-2

Poly (ethylene glycol) monomethyl ether (average molecular weight (average weighted) Mn = 350 g / mol) (company Sigma-Aldrich Chemie).

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Component D2-3

Polyethylene glycol monomethyl ether (weight molecular average (average weighted) Mn 2000) (company Sigma-Aldrich Chemie).

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Component AND

Oligophosphate based on bisphenol A

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fifteen

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Component F

Polytetrafluoroethylene powder, CFP 6000 N, Du Pont company.

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Component G1

Pentaerythritol Tetraestearate.

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Component G2

Phosphite Stabilizer

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Component G3

Tetraphenylphosphonium phenolate.

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Preparation and testing of molding masses according to invention

In a twin screw extruder press (ZSK-25) (Werner and Pfleiderer) combine and the initial substances cited in Table 2 are granulated at a speed of 225 rpm and a flow of 20 kg / h at a machine temperature of 260ºC. The total lot size amounts to 8 kg respectively. Example 1 represents the comparison without adding phyllosilicate, Example 2 contains as comparison a cationically modified phyllosilicate that can Obtained commercially, and Example 3 contains the stock mixture of phyllosilicate polycarbonate previously described.

The prepared granules are processed in a injection molding machine to give the specimens corresponding (mass temperature 260 ° C, temperature of 80ºC mold, 240 mm / s cast front speed) and are characterized  according to ISO 1133 (MVR), ISO 5660-1 (calorimetry of cone) and ASTM E 662 (smoke density) and by analysis thermogravimetric (TGA).

The determination of the volumetric index of merger (MVR value, Melt volume-flow rate) is Performs according to ISO 1133 (260ºC; 5 kg).

Measurement determination in calorimeter cone (50 kW / m2, 60 mm distance) is performed according to ISO 5660-1

The smoke density determination is Performs according to ASTM E 662 (with ignition flame d = 3 mm).

The performance of thermogravimetric analysis (TGA) was performed with a TGA / SDTA 851e (Mettler-Toledo). Approximately 10 mg was weighed of the samples and washed under a gas mixture of 20% of oxygen in helium with a flow rate of 80 ml / min 30 min at 25 ° C and at then they were heated to 800 ° C with a heating rate  of 5 K / min. During the total measurement, the weight change and masses were recorded on the spectrometer of masses. Table 2 specifies the temperature range for the decomposition that was deduced from the weight loss in Measured percentage or weight loss rate (in% min -1). He initial value corresponds to the start of decomposition, the final value with the end of decomposition.

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(Table goes to page next)

TABLE 2

16

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From Table 2 it is clear that through addition of the mother mixture of phyllosilicate-polycarbonate according to the invention (Example 3) decreases smoke density according to ASTM E 662, decreases the maximum heat release rate (Heat Release, determined by cone calorimetry) and also increases the decomposition temperature (thermogravimetric analysis), the volumetric melt index remains unchanged (value of MVR) compared to the no-load molding mass (Example Comparative 1) in the framework of measurement accuracy.

In addition, compared to the use of cationically modified phyllosilicates (Comparative Example 2) are reaches a lower MARHE value (MARHE = Maximum Average Rate of Heat emission; maximum average heat emission). Molding mass according to Comparative Example 2 containing phyllosilicate cationically modified gives a clearly high MVR value at comparison with Comparative Example 1 and Example 3 according to the invention, which indicates a high degradation of molecular weight of the polycarbonate matrix.

Claims (15)

1. Composition it contains

TO)

a polycarbonate and / or polyester carbonate aromatic,

B)

if necessary a modifier of resistance to impact,

C)

if necessary a homo and / or copolymer thermoplastic,

D)

a layered compound that is modified with poly (alkylene oxide) with an average weighted molecular weight of 106 to 20,000 g / mol by a melt process without solvent, and

AND)

if necessary a phosphorus compound.

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2. Composition according to claim 1 that contains

TO)

30 to 99.9 parts by weight of polycarbonate and / or polyester aromatic carbonate,

B)

0 to 60 parts by weight of a graft polymer rubber modified,

C)

0 to 30 parts by weight of homo and / or copolymer,

D)

0.1 to 40 parts by weight of a layered compound that it is modified with poly (alkylene oxide) with a molecular weight Weighted average of 106 to 20,000 g / mol by mass process molten without solvent, and

AND)

0 to 30 parts by weight of compound match,

the sum of the parts being by weight of the components A, B, C, D and E normalized to 100.

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3. Composition according to claim 1 containing layered compounds with an average thickness of 0.3 to
10 nm 4. Composition according to claim 3 which it contains compounds in layers in which the layers have a diameter from 5 to 10,000 nm. 5. Composition according to one of the claims 1 to 4 containing a layered compound that is modified with poly (alkylene oxide) with a molecular weight weighted average of 106 to 20,000 g / mol and at least one other polymer by a melt process without solvent. 6. Composition according to one of the claims 1 to 5, wherein as component B) a graft polymer modified with rubber

B.1

65 to 95% by weight based on B) of a mixture from

B.1.1

50 to 99% by weight referred to B.1) of at least one monomer selected from the group of aromatic compounds of vinyl and vinyl aromatic compounds substituted at the core Y

B.1.2

1 to 50% by weight referred to B.1) of at least one monomer selected from the group of vinyl cyanides, esters (C 1 -C 8) alkyl of acid (meth) acrylic and carboxylic acid derivatives unsaturated

in

B.2

5 to 35% by weight referred to B) of one or more bases graft with a glass transition temperature ≤ -10 ° C.

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7. Composition according to claim 6, in which monomers B.1.1) are styrene and monomers B.1.2) acrylonitrile 8. Composition according to claim 7, in which graft base B.2) contains dienic rubber.

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9. Composition according to one of the preceding claims containing a (co) polymer from

C.1

50 to 99% by weight based on the (co) polymer of at least one monomer selected from the group of compounds vinyl aromatics, vinyl aromatic compounds substituted in the nucleus and alkyl esters (C 1 -C 8) of (meth) acrylic acid and

C.2

1 to 50% by weight based on the copolymer of al minus a monomer selected from the group of vinyl cyanides, (C 1 -C 8) alkyl esters of acid (meth) acrylic, unsaturated carboxylic acids and derivatives of unsaturated carboxylic acids.

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10. Composition according to one of the claims 1 to 9, wherein to modify the compound in layers by a solvent-free melt process

(one)

in a first stage, the layered compound is mixture with poly (alkylene oxide) with a weighted molecular weight medium 106 to 20,000 g / mol or a mixture of poly (alkylene oxide) with an average weighted molecular weight of 106 to 20,000 g / mol and at minus another organic polymer,

(2)

in a second stage, the mixture is heated to a temperature above the melting temperature of the poly (oxide alkylene) used with a weight average molecular weight of 106 to 20000 mol or the mixture of polymers used of poly (oxide of alkylene) with an average weighted molecular weight of 106 to 20,000 g / mol and at least one other organic polymer.

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11. Composition according to one of the preceding claims containing additives selected from at least one of the group of flame retardants, drip agents, lubricating agents and mold release agents, nucleating agents, antistatic, stabilizers, fillers and reinforcing substances, dyes and pigments 12. Method for preparing thermoplastic molding doughs from compositions according to one of the preceding claims, characterized in that

(i)

in a first stage, the layered compound is modifies with poly (alkylene oxide) with a molecular weight Weighted average of 106 to 20,000 g / mol by mass process molten without solvent,

(ii)

in a second stage, the compound mixture Layered obtained from (i) is mixed with component (A) and given the other components selected from the group of (B), (C), (E), (F) and (G) and

(iii)

In a third stage, the mixture of (ii) is combined in molten mass and extruded in molten mass at temperatures of 200ºC to 300ºC.

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13. Use of the compositions according to one of the claims 1 to 11 for the manufacture of bodies molded 14. Molded bodies containing a composition according to one of claims 1 to 11. 15. Molded bodies according to claim 14, characterized in that the molded body is a part of a vehicle, rail vehicle, aircraft or water vehicle or a housing of electrical devices containing small transformers, housing for apparatus for processing and transmission of information, housing and coating of medical devices, massage devices and housing for them, children's toy vehicles, flat wall panels, housing for safety devices, heat-transported containers, molded parts for sanitary and bathroom equipment, grid protection for ventilation holes or a housing for gardening tools.